Transparent heat-mirror

ABSTRACT

Transparent heat-mirrors are disclosed which are comprised of composite films. These films include a discrete and continuous layer of metallic silver sandwiched between a transparent, outer, protective, anti-reflection layer and a transparent, phase-matching layer. This combination of layers is chosen to provide high solar transmission with minimum loss of thermal radiation. Transparent heat-mirrors are useful in the collection and trapping of solar energy, and in other applications where it is desired or necessary to have high infrared reflectivity with high solar transmission.

GOVERNMENT SUPPORT

The invention described herein was made in the course of or under acontact from the United States Air Force.

RELATED APPLICATIONS

This application is a continuation of application Ser. No. 804,664,filed on Dec. 2, 1985, now U.S. Pat. No. 4,721,349 which is acontinuation of Ser. No. 365,533 filed Apr. 5, 1982, which issued onDec. 3, 1985 as U.S. Pat. No. 4,556,277, which is a continuation of Ser.No. 690,696 filed May 27, 1976, which issued July 6, 1982, as U.S. Pat.No. 4,337,990, which is a continuation-in-part of Ser. No. 498,169 filedAug. 16, 1974, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is in the field of heat-mirrors and more particularly inthe field of heat-mirrors having high infrared reflectivity and highvisible transmission.

2. Description of the Prior Art

Heat-mirrors that reflect radiation in the infrared spectrum whiletransmitting radiation in the visible spectrum have importantapplications as transparent thermal insulators for furnaces, windows inbuildings, and solar-energy collection. In the field of solar energy,for example, it is desirable to collect sunlight efficiently and toconvert it into heat energy. Traditional strategy for optimizing thermalenergy collection with a flat-plate collector has been concentrated onthe absorber wherein the sun's radiant energy is converted into heat. Ifthe absorber is a black body, it converts all of the incident radiationinto heat, but it also converts the heat to infrared radiation that isreradiated back into space. Usual strategy is to design a material thathas high absorptivity for radiation from the sun, but that has lowemissivity for infrared radiation. For solar energy farms to collectsolar energy for thermal to electrical power conversion, this requires amaterial that has a low emissivity for infrared radiation from a body atabout 800° K. Moreover, the absorber material possessing theseproperties must be stable at such temperatures for long periods of time,must withstand thermal variations from cold winter nights to 800° K.during the day; and must also be cheap to manufacture and to maintain inthe field. The probability of success with this strategy alone appearsminimal.

An alternate strategy is to introduce a heat-mirror that is separatedfrom the heat absorber and will therefore be much cooler. Heat-mirrorsdesigned for this purpose have been fabricated from tin-doped indiumoxide and antimony-doped tin oxide. See Groth, R. and Kauer, E., PhilipsTech. Rev., 26, 105 (1965); Groth, R., Phys. Stat. Solid, 14, 69 (1966);Fraser, D. B. and Cook, H. D., J. Electrochem. Soc., 119, 1368 (1972);Vossen, J. L. and Poliniak, E. S., Thin Solid Films, 13, 281 (1972);Mehta, R. R. and Vogel, S. F., J. Electrochem. Soc., 119, 752 (1972);and Vossen, J. L., RCA Review, 32, 289 (1971). Although these materialsare stable in air up to 400°-500° C. and can have visible transmissionsas high as 80-90% on Pyrex glass, their infrared reflectivities ataround 10 micrometers (for room temperature radiation) are only betweenabout 80-90%, which are much lower than desirable.

Kirchoff's Law states that the sum of transmission (Tr), reflectivity(R) and absorptivity (A) for a given wavelength must be equal to one, orTr+R+A=1.0. For transparent heat-mirrors, solar transmission must behigh, and hence the reflectivity and absorptivity must be low. In theinfrared, however, the heat-mirror must have high reflectivity and sotransmission and absorptivity in the infrared must be low. UsingKirchoff's Law, and assuming that transmission in the infrared isminimal, it can be shown that thermal radiation losses are directlyproportional to (1-R), meaning that it is important to have an infraredreflectivity as close to 100% as possible while maintaining the solartransmission as high as possible.

Other heat-mirrors are also known. See Holland, L. and Siddall, G.,British Journal of Applied Physics, 9, 359 (1958). These authors testedvarious metal oxide films on glass, gold films on glass, and gold filmssandwiched between either bismuth oxide or silicon monoxide layers. Theyfound that the optimum performance was obtained with multilayercomposite having a 130 Å gold layer sandwiched between two 450 Å bismuthoxide coatings. Nevertheless, the transmittance of this composite wasfound to be only 73% for green light and the reflectance was only 74% inthe near infrared region, values which are not satisfactory for solarenergy collection and for many other applications where higher infraredreflectivity coupled with higher transmissions in the visible arerequired.

SUMMARY OF THE INVENTION

In one embodiment, the invention comprises transparent heat-mirrorsformed from composite films. These films have a layer of metallic silverwith a thickness of about 30-200 Å. A transparent, protective,anti-reflection layer is deposited on the outer surface of the silverlayer to provide environmental protection as well as the desired opticalproperties to the film composite. A transparent, phase-matching, bondinglayer is deposited on the other side of the silver layer which works incombination with the outer, anti-reflection coating to minimizereflection losses of solar radiation. It also serves as a nucleation andbonding layer.

One suitable embodiment of a transparent heat-mirror according to thisinvention can be formed by depositing 180 Å titanium dioxide coatings oneach side of a 180 Å metallic silver layer. In this embodiment, theouter, anti-reflection layer and the phase-matching layer are identical,i.e., 180 Å titanium doxide; nevertheless, this is not a requirement andthese layers could be formed from different compounds and/or havedifferent thicknesses.

Transparent heat-mirrors prepared according to this invention havesignificant advantages over those heretofor known. They are, forexample, environmentally stable. Additionally, they can be manufacturedusing small quantities of readily available materials by adaptation ofknown techniques.

The most significant advantage is, of course, the outstanding opticalproperties which can be obtained. Metallic silver has a very highinfrared reflectivity and the use of the disclosed anti-reflection andphase-matching layers serves to dramatically increase the solartransmission without concomitantly lowering infrared reflectivity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates schematically a transparent heat-mirror according tothis invention;

FIG. 2 illustrates graphically the actual measured reflectivity andtransmission of a transparent heat-mirror formed from a 180 Å metallicsilver layer sandwiched between 180 Å titanium dioxide layers and placedon a one millimeter thick substrate of Corning No. 7059 glass;

FIG. 3 illustrates graphically the computed theoretical reflectivity andtransmission of a transparent heat-mirror formed from a metallic silverlayer sandwiched between titanium dioxide layers and placed on a onemillimeter thick substrate of Corning No. 7059 glass; and,

FIG. 4 illustrates graphically the measured variation of opticaltransmission with angle of incidence.

DESCRIPTION OF PREFERRED EMBODIMENTS

As used herein, the following terms are defined to mean:

"Infrared radiation" means electromagnetic radiation having a wavelengthabove 0.8 micrometers;

"Visible radiation" means electromagnetic radiation having a wavelengthof from about 0.4 to 0.8 micrometers;

"Transparent" means transparent to visible radiation unless otherwisestated;

"heat-mirror" means an element which has high reflectivity for infraredradiation; and,

"Solar spectrum" means the range of wavelengths received from the sun,which will vary with many factors, of course, but does include visibleradiation.

Referring now to the Figures in more detail, the basic configuration ofa transparent heat-mirror as described herein is illustrated in FIG. 1.Transparent heat-mirror 10 is formed from a metallic silver layer 11; atransparent, outer, protective, anti-reflection layer 12; and atransparent phase-matching layer 13. Because these layers are thin, asupporting transparent substrate 14, which may be glass, quartz, ortransparent plastic, for example, is used. Outer layer 12 need not bethe top layer in a composite, but is is always upper in the sense ofbeing positioned on the side of the silver layer which has incidentradiation thereon.

Known techniques can be used to deposit each of the layers in thecomposite films. It has been found, however, that it is necessary todeposit these layers so that they are discrete and continuous. Ingeneral, the layers should be deposited to minimize interdiffusiontherebetween to provide discrete layers with very high infraredreflectivity and visible transmission. The exact method of depositionwill depend upon parameters such as the various materials used for eachof the layers, their thicknesses, the availability of equipment, etc.Some suitable techniques include RF sputtering, DC reactive sputtering,thermal evaporation, electron beam evaporation and chemical vapordeposition; those skilled in the art will know other suitable methods orwill be able to ascertain them using no more than routineexperimentation.

Metallic silver is used as the inner layer because of its outstandingoptical properties for heat-mirrors. It offers high reflectivity toinfrared radiation together with high transmission to solar radiationproviding its reflection losses are minimized. Although high puritymetallic silver films are preferred, certain impurities and/or alloyingmetals can be tolerated as long as they do not significantly reduce theinfrared reflectivity or significantly increase the visibleabsorptivity.

Some of the advantages of silver, compared to other metals, have beendocumented. For example, it has been shown that both copper and goldabsorb about 50% of the incident energy for wavelengths lower than 0.5um, whereas silver does not absorb appreciably for wavelengths above 0.3um. See Fan and Bachner, "Transparent Heat Mirrors for Solar EnergyApplications," Applied Optics, 15, 1012 (Apr., 1976).

The exact thickness of the metallic silver layer will depend upon thespecific application, but in general layers thinner than about 30 Å aredifficult to deposit as continuous, discrete films, while layers thickerthan about 200 Å are not suitable because of their lower solartransmission. The exact thickness, within this range, depends upon thespecific application. For use in thermal power conversion, as isrequired in many solar energy applications, it has been calculated, forexample, that the preferred silver layer thickness is from about 150 |to about 200 Å. Somewhat thinner layers, such as down to about 50 Å, arebelieved to be more suitable for domestic, insulating windows. Solarenergy panels which provide heat for space heating or hot water heatingare believed to require silver layers from about 100 Å to about 150 Å.Transparent windows for ovens and furnaces will have silver layers withthicknesses maximized for the appropriate temperatures in the ovens orfurnaces, but in general, these layers will be within the 30-200 Årange.

Suitable materials for the outer protective coating are materials whichare transparent to solar and infrared radiation in the thicknesses used,are themselves environmentally stable, are capable of serving asprotective layers to protect the silver layer from adverse environmentalelements. Environmental stability means that the properties of thesematerials, including the optical properties, do not appreciablydeteriorate upon exposure to air, water and temperatures up to 200 Å C.Additionally, these materials serve as anti-reflection coatings tominimize the reflection of visible light by the silver layer, and thesematerials preferably have high indices of refraction, such as above 1.4.

Some suitable materials for the outer anti-reflection layers include,but are not limited to, titanium dioxide, silicon dioxide, siliconmonoxide, bismuth oxide, tin oxide, indium oxide, chromium oxide, zincsulfide and magnesium fluoride. Other suitable materials are known tothose skilled in the art, or are ascertainable by no more than routineexperimentation. Titanium dioxide is a preferred material because of itshigh refractive index and because it has been found to have minimuminterdiffusion with silver, even at elevated temperatures such as 200 ÅC., if care is taken to deposit discrete layers.

Suitable materials for the phase-matching layer are transparentmaterials which cooperate with the outer anti-reflection coating tominimize visible light reflection losses by the silver layer. Thetransparent materials suitable for the outer, anti-reflection layer arealso suitable for the phase-matching layer, and titanium dioxide is alsoa preferred material for this layer. An additional requirement is thatfilms prepared be adherent to transparent substrates, such as glass,quartz, plastic, etc. It is particularly preferred to have materialswhich offer better adherence to such substrates than silver, but towhich silver adheres well, and which serve as nucleation layers forsilver. The phase-matching layer can be formed from the same material asthe outer anti-reflecting layer, or from a different material in whichcase it would probably have a different thickness. As mentioned above,the primary purpose of the phase-matching layer is to cooperate with theanti-reflection coating to increase the transmission of visible or solarradiation through the entire composite film.

The thicknesses for the outer, anti-reflection layer and thephase-matching layer are chosen to maximize solar transmission andinfrared reflectivity. It should be noted that the thickness of theanti-reflection layer is not chosen by using quarter-wave theory. It hasbeen found that a thickness of from about 150 Å to about 500 Å issuitable for the outer, protective coating. The thickness of thephase-matching layer is then chosen based upon a number ofconsiderations such as whether it is desired to achieve the optimumsolar transmission, the optimum ratio of transmission to thermalreflectivity or some combination between these optimized values.

Two criteria have been established to help in selecting the specificthicknesses for the outer protective layer and the phase-matchinglayers.

These criteria involve two heat-mirror parameters which are defined as:##EQU1## where TR(λ)=Transmission of heat-mirror at wavelength λ

R(λ)=Reflectivity of heat-mirror at wavelength λ

A(λ)=Solar energy spectrum

W_(B) (T_(B),λ)=Energy distribution for a blackbody at an operatingtemperature T_(B).

These definitions assume that the heat-mirror is used in conjunctionwith a perfect (i.e., black) absorber, which absorbs all the solarradiation transmitted and also all the infrared radiation reflected bythe heat-mirror.

These definitions facilitate comparison with the known quantities, α andε, which are used to characterize selective absorbers. It can also beseen from these definitions, that α_(eff) is the effective transmissionobtained by integrating over the spectrum from 0.25 μm to 2.5 μm.Similarly, ε_(eff) is the effective reflectivity heat loss (1-r)obtained by integrating over the spectrum from 1.0 μm to 100 μm. Thesevalues allow heat-mirror properties to be evaluated quantitatively as afunction of the outer and phase-matching layer thicknesses for anychosen operating temperature. Typically, the computations required forsuch evaluations are performed with the aid of a computer.

Transparent heat-mirrors, according to this invention, must have outerprotective and phase-matching layers which provide, in combination withthe silver layer, an α_(eff) of at least about 0.5 and an α_(eff)/ε_(eff) of at least about 5. Preferably α_(eff) is above about 0.8 andα_(eff) /ε_(eff) is above about 10.

In most cases, the optical properties desired can be achieved bychoosing a phase-matching layer of between about 150 Å and about 500 Å.Typically, the preferred thickness for the phase-matching layer iswithin about 10% of the thickness of the anti-reflection coating.

Transparent heat-mirrors according to this invention have three criticallayers. These are the silver layer, an outer protective layer, and aphase-matching layer. It should be recognized that additional layers canbe present if desired. The preferred embodiments, however, have onlythree layers (disregarding the substrate), and particularly preferredembodiments have a single silver film sandwiched between single titaniumdioxide films on either side thereof.

Transparent heat-mirrors as described herein are useful for a number ofapplications. They are, for example, useful in the collection andtrapping of solar energy. They can also be used for transparent,insulation for buildings, furnaces, etc. In many of these uses, it isonly the "visible" part of the solar spectrum that is of concern.Nevertheless, the heat-mirrors, as defined herein, are useful for suchapplications. Other uses will be apparent to those skilled in the artwherein it is desired to have materials which have high infraredreflectivity and high solar or visible transmission.

The invention can be further understood by referring to the followingexamples.

EXAMPLE 1 PREPARATION OF A TRANSPARENT HEAT-MIRROR

A transparent heat-mirror was prepared by RF sputtering a titaniumdioxide/silver/titanium dioxide multilayer film onto Corning No. 7059glass. The RF sputtering system used was a LN₂ -trapped, turbopumpedunit (base pressure approximatley 5 ×10⁻⁷ Torr) with a MaterialsResearch Corporation three-target turret head sputtering module. Thetargets were commercially prepared five inch diameter discs of silverand titanium dioxide. A multilayered film was grown on a glass substrateresting on a water-cooled stainless steel platform in a single pumpdownwith the following sequence.

The titanium dioxide target was presputtered at 1.6 watt/cm.sup. 2 in anargon-oxygen mixture (10 volume percent oxygen) for 15 minutes, followedby 15 minutes of presputtering in argon gas only. The flow rate ofargon-oxygen and argon was kept at 74 cc/min. and the sputteringpressure was maintained between 7-10×10⁻ 3 Torr.

The titanium dioxide film was then sputtered at 0.8 watt/cm.sup. 2 ontothe glass substrate for 71/2 minutes in argon at a 74 cc/min flow rateand pressure of 7-10×10⁻³ Torr. The thickness of the titanium dioxidecoating produced was approximately 180 Å.

Metallic silver was then deposited over the titanium dioxide film bysputtering for 35 seconds at 0.4 watt/cm.sup. 2 in argon at 74 cc/minand a pressure of 7-10×10⁻³ Torr. This produced a metallic silver 180 Åthick.

An outer layer of titanium dioxide was then deposited at 0.8watt/cm.sup. 2 for 71/2 minutes in argon gas at 74 cc/min and a pressureof 7-10×10⁻³ Torr. This titanium dioxide layer also had a thickness ofabout 180 Å.

The transmission to visible light and reflectivity of infrared lightwere tested using conventional spectrophotometric techniques which hadan accuracy of ±1%. The data obtained are plotted in FIG. 2 from whichit can be seen that the transparent heat-mirror of this Example had aninfrared reflectivity of about 98-99% at 10 micrometers and atransmission of about 84% at 0.5 micrometers.

Theoretical curves for the reflectivity of infrared light andtransmission of visible light for a titanium dioxide/silver/titaniumdioxide heat-mirror are shown in FIG. 3. These were generated by acomputer and are based on multilayer matrix formulation. See Heaven, O.S., "Optical Properties of Thin Solid Films," Dover Publications, p. 69(1965). Published optical constants for titanium dioxide and silver wereused. See Moses, A. J., "Optical Materials Properties," IFI/Plenun DataCorp., p. 97 (1971); and Johnson, P. B. and Christy, R. W., Phys. Rev.,B6, 4370 (1972).

It can be seen by comparing FIG. 2 and 3 that the actual measured valuesare close to the theoretically predicted. This is evidence that thelayers are discrete and that interdiffusion has been minimized.

EXAMPLE 2 EFFECT OF ANGLE OF INCIDENCE

The effect of angle of incidence on optical transmission of theheat-mirror prepared in Example 1 was tested on a conventionalspectrophotometer having accuracy to ±1%. No appreciable differenceswere noted between 0° and 20° The results for 0° and 40° are plotted inFIG. 4 from which it can be seen that the differences are minimal.

EXAMPLE 3 ENVIRONMENTAL STABILITY--ELEVATED TEMPERATURES

The environmental stability of the transparent heat-mirror prepared inExample 1 was tested by maintaining it in air at 200° C. for 48 hours.No appreciable degradation in its optical properties were seen.Maintaining the composite at 300° C. for 16 hours produced only smallchanges in the optical properties.

EXAMPLE 4 ENVIRONMENTAL STABILITY--WATER

The environmental stability of the composite prepared in Example 1 wasfurther tested by running tap water across the surface of the compositefor 5 to 10 minutes. The composite was then examined under an opticalmicroscope using a bright field and no changes were noted. Uponmeasuring the transmission of visible light and reflectivity to infraredlight no significant changes were noted.

EXAMPLE 5 AUGER PROFILE

The transparent heat-mirror of Example 1 was characterized by Augerprofile spectroscopy using a Physical Electronics Laboratory Inc. Augerspectrometer. The data obtained indicated that each layer of thecomposite film was discrete.

EXAMPLE 6 HEAT-MIRRORS OPTIMIZED FOR VARIOUS CONDITIONS

Optimum thicknesses for outer protective layers (t_(o)) andphase-matching layers (t_(pm)) were calculated using a computer forvarious conditions and for two different materials. These conditionswere:

Case 1 - For equal layers, maximum α_(eff) /ε_(eff) ratio;

Case 2 - For equal layers, maximum α_(eff) ;

Case 3 - Maximum α_(eff) /ε_(eff) ratio;

Case 4 - Maximum α_(eff).

These values were computed for outer protective and phase-matchinglayers formed from both titanium dioxide and zinc sulfide. Air mass 2and an operating temperature of 121° C. were used in these calculations.The results are presented in Tables I and II, with a correction havingbeen made to eliminate the effect of the glass (SiO₂) substrate.

                                      TABLE I                                     __________________________________________________________________________    TiO.sub.2 /Ag/TiO.sub.2                                                       Case 1          Case 2      Case 3            Case 4                                    α.sub.eff /                                                                t.sub.o,t.sub.pm                                                                       α.sub.eff /                                                                t.sub.o,t.sub.pm                                                                        α.sub.eff /                                                                              α.sub.eff           t.sub.Ag (Å)                                                                  α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                (Å)                                                                          α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                (Å)                                                                          α.sub.eff                                                                   ε.sub.eff                                                                ε.sub.eff                                                                t.sub.o, (Å)                                                                  t.sub.pm (Å)                                                                  α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                t.sub.o                                                                           t.sub. pm                                                                     (Å)            __________________________________________________________________________     30 .869                                                                             .126                                                                              6.9                                                                             377                                                                              .870                                                                             .126                                                                              6.9                                                                             389                                                                              .868                                                                              .126                                                                              6.9                                                                             359 392 .870                                                                             .126                                                                              6.9                                                                             385 394                 50 .905                                                                             .0635                                                                            14.3                                                                             359                                                                              .906                                                                             .0636                                                                            14.2                                                                             372                                                                              .905                                                                              .0635                                                                            14.3                                                                             352 372 .906                                                                             .0636                                                                            14.2                                                                             373 370                100 .876                                                                             .0260                                                                            33.7                                                                             359                                                                              .877                                                                             .0261                                                                            33.6                                                                             364                                                                              .876                                                                              .0260                                                                            33.7                                                                             357 361 .877                                                                             .0261                                                                            33.6                                                                             367 360                150 .746                                                                             .0149                                                                            46.9                                                                             337                                                                              .746                                                                             .0159                                                                            46.9                                                                             342                                                                              .747                                                                              .0159                                                                            47.0                                                                             345 324 .747                                                                             .0159                                                                            47.0                                                                             353 324                200 .613                                                                             .0114                                                                            53.8                                                                             310                                                                              .613                                                                             .0114                                                                            53.8                                                                             314                                                                              .615                                                                              .0114                                                                            53.9                                                                             320 295 .615                                                                             .0114                                                                            53.9                                                                             328 296                250 .487                                                                             .0089                                                                            54.7                                                                             290                                                                              .487                                                                             .0089                                                                            54.7                                                                             293                                                                              .489                                                                              .0089                                                                            54.9                                                                             302 275 .489                                                                             .0089                                                                            54.9                                                                             306 274                300 .374                                                                             .0074                                                                            50.5                                                                             268                                                                              .374                                                                             .0074                                                                            50.5                                                                             272                                                                              .376                                                                              .0074                                                                            50.8                                                                             278 251 .376                                                                             .0074                                                                            50.8                                                                             286 255                400 .209                                                                             .0058                                                                            36.0                                                                             230                                                                              .206                                                                             .0058                                                                            35.5                                                                             231                                                                              .211                                                                              .0058                                                                            36.4                                                                             241 220 .211                                                                             .0058                                                                            36.4                                                                             247 221                500 .110                                                                             .0051                                                                            21.6                                                                             212                                                                              .110                                                                             .0051                                                                            21.6                                                                             214                                                                              .110                                                                              .0051                                                                            21.6                                                                             221 207 .110                                                                             .0051                                                                            21.6                                                                             224 208                __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    ZnS/Ag/ZnS                                                                    Case 1          Case 2      Case 3            Case 4                                    α.sub.eff /                                                                t.sub.o,t.sub.pm                                                                       α.sub.eff /                                                                t.sub.o,t.sub.pm                                                                        α.sub.eff /                                                                              α.sub.eff           t.sub.Ag (Å)                                                                  α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                (Å)                                                                          α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                (Å)                                                                          α.sub.eff                                                                   ε.sub.eff                                                                ε.sub.eff                                                                t.sub.o (Å)                                                                   t.sub.pm (Å)                                                                  α.sub.eff                                                                  ε.sub.eff                                                                ε.sub.eff                                                                t.sub.o                                                                           t.sub. pm                                                                     (Å)            __________________________________________________________________________     30 .907                                                                             .123                                                                              7.4                                                                             404                                                                              .911                                                                             .124                                                                              7.3                                                                             438                                                                              .907                                                                              .123                                                                              7.4                                                                             394 417 .911                                                                             .124                                                                              7.3                                                                             432 446                 50 .933                                                                             .0623                                                                            15.0                                                                             412                                                                              .934                                                                             .0623                                                                            15.0                                                                             424                                                                              .933                                                                              .0623                                                                            15.0                                                                             410 415 .934                                                                             .0623                                                                            15.0                                                                             427 475                100 .858                                                                             .0255                                                                            33.6                                                                             432                                                                              .858                                                                             .0255                                                                            33.6                                                                             436                                                                              .858                                                                              .0255                                                                            33.6                                                                             429 432 .858                                                                             .0256                                                                            33.5                                                                             437 432                150 .666                                                                             .0156                                                                            42.7                                                                             453                                                                              .701                                                                             .0156                                                                            44.9                                                                             411                                                                              .702                                                                              .0156                                                                            45.0                                                                             418 383 .702                                                                             .0156                                                                            45.0                                                                             420 387                200 .553                                                                             .0112                                                                            49.4                                                                             379                                                                              .553                                                                             .0112                                                                            49.4                                                                             383                                                                              .555                                                                              .0112                                                                            49.6                                                                             393 354 .555                                                                             .0112                                                                            49.6                                                                             398 354                300 .311                                                                             .0073                                                                            42.6                                                                             343                                                                              .311                                                                             .0073                                                                            42.6                                                                             347                                                                              .313                                                                              .0073                                                                            42.9                                                                             360 313 .313                                                                             .0073                                                                            42.9                                                                             362 312                400 .161                                                                             .0057                                                                            28.2                                                                             295                                                                              .161                                                                             .0057                                                                            28.2                                                                             297                                                                              .162                                                                              .0057                                                                            28.4                                                                             320 275 .162                                                                             .0057                                                                            28.4                                                                             324 275                500 .081                                                                             .0050                                                                            16.2                                                                             268                                                                              .081                                                                             .0050                                                                            16.2                                                                             269                                                                              .081                                                                              .0050                                                                            16.2                                                                             286     .081                                                                             .0050                                                                            16.2                                                                             288 259                __________________________________________________________________________

EXAMPLE 7 HEAT-MIRRORS HAVING OUTER PROTECTIVE AND PHASE-MATCHING LAYERSARBITRARILY CHOSEN

Values for αeff and εeff were computed for heat-mirrors containingsilver sandwiched between titanium dioxide and silver sandwiched betweenzinc sulfide with outer protective and phase-matching layers arbitrarilychosen to each have thicknesses of 500, 1000 and 1500 Å. A correctionwas made to eliminate the effect of a glass (SiO₂) substrate. Air mass 2conditions and operating temperature of 121° C. were selected. Theresults are presented in Tables III and IV. It is readily apparent fromthe data obtained that using these thicknesses, which are typical ofthicknesses which might be chosen using quarterwave theory, does notproduce optimum results.

                  TABLE III                                                       ______________________________________                                        TiO.sub.2 /Ag/TiO.sub.2 /S.sub.1 O.sub.2                                                                          α.sub.eff /                         t.sub.Ag (Å)                                                                        t.sub.o,t.sub.pm (Å)                                                               α.sub.eff                                                                          ε.sub.eff                                                                   ε.sub.eff                         ______________________________________                                        100        500     .806       .0266 30.3                                                1000     .674       .0299 22.5                                      200        500     .524       .0118 44.4                                                1000     .419       .0138 30.4                                                1500     .361       .018  20.6                                      300        500     .277        .00776                                                                             35.7                                                1000     .237        .00952                                                                             24.1                                                1500     .200       .0133 15.0                                      400        500     .132       .0061 21.6                                                1000     .127       .0078 16.3                                                1500      .1019     .0115 8.9                                       500        500      .0600     .0054 11.1                                                1000      .0647     .0071 9.1                                                 1500      .0493     .0107 4.6                                       ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        ZnS/Ag/ZnS                                                                                                        α.sub.eff /                         t.sub.Ag (Å)                                                                        t.sub.o,t.sub.pm (Å)                                                               α.sub.eff                                                                          ε.sub.eff                                                                   ε.sub.eff                         ______________________________________                                        100        500     .845       .0256 33.0                                                1000     .645       .0265 24.3                                                1500      .5596     .0279 20.1                                      200        500     .521       .0112 46.5                                                1000     .368       .0115 32.                                                 1500     .328       .0120 27.3                                      300        500     .276        .00735                                                                             37.6                                                1000     .187        .00751                                                                             24.9                                                1500     .173        .00777                                                                             22.3                                      ______________________________________                                    

EXAMPLE 8 EFFECT OF PHASE-MATCHING LAYER

The transmission (T) at 0.5 μm and reflectivity at 5.0 μm werecalculated for: (1) a silver film 180 Å thick coated on one side onlywith a titanium dioxide layer 180 Å thick; and (2) the same silver filmcoated on both sides with titanium dioxide layers 180 Å thick. Thevalues found were:

    ______________________________________                                                          T(0.5 μm)                                                                          R(05.0 μm)                                       ______________________________________                                        180 Å TiO.sub.2 /180 Å Ag                                                                 76%       98%                                             180 Å TiO.sub.2 /180 Å Ag/180 Å TiO.sub.2                                             89%       98%                                             ______________________________________                                    

A significant increase in visible light transmission can be seen whenthe phase-matching layer is present.

What is claimed is:
 1. A composite film comprising a continuous,discrete metallic layer sandwiched between two continuous, discrete,transparent layers each having a thickness of greater than about 150 Å,said metallic layer substantially comprised of silver, said metallic andtransparent layers having thicknesses that cooperate to provide saidcomposite film with significantly higher solar energy transmissioncompared to the metallic layer alone and with high infraredreflectivity.
 2. A composite film comprising a continuous, discretemetallic layer sandwiched between two or more continuous, discrete,transparent layers each having a thickness of greater than about 150Å,said metallic layer substantially comprised of silver, said metallicand transparent layers having thicknesses that cooperate to provide saidcomposite film with significantly higher solar energy transmissioncompared to the metallic layer alone and with high infraredreflectivity.
 3. A composite film comprising a continuous, discretemetallic layer sandwiched between two continuous, discrete, transparentlayers each having a thickness of greater than about 150 Å, saidmetallic layer consisting essentially of silver, said metallic andtransparent layers having thicknesses that cooperate to provide saidcomposite film with significantly higher solar energy transmissioncompared to the metallic layer alone and with high infraredreflectivity.
 4. A composite film comprising a continuous, discretemetallic layer sandwiched between two or more continuous, discrete,transparent layers each having a thickness of greater than about 150 Å,said metallic layer consisting essentially of silver, said metallic andtransparent layers having thicknesses that cooperate to provide saidcomposite film with significantly higher solar energy transmissioncompared to the metallic layer alone and with high infraredreflectivity.
 5. A composite film comprising a continuous, discretemetallic layer sandwiched between two continuous, discrete, transparentlayers each having a thickness of greater than about 150 Å, saidmetallic layer comprising silver and one or more alloying metals, whichdo not significantly reduce the infrared reflectivity or significantlyincrease the visible absorptivity of the metallic layer, said metallicand transparent layers having thicknesses that cooperate to provide saidcomposite film with significantly higher solar energy transmissioncompared to the metallic layer alone and with high infraredreflectivity.
 6. A composite film comprising a continuous, discretemetallic layer sandwiched between two continuous, discrete, transparentlayers each having a thickness of greater than about 150 Å, saidmetallic layer substantially comprising silver and one or more alloyingmetals, which do not significantly reduce the infrared reflectivity orsignificantly increase the visible absorptivity of the metallic layer,said metallic and transparent layers having thicknesses that cooperateto provide said composite film with significantly higher solar energytransmission compared to the metallic layer alone and with high infraredreflectivity.
 7. In the formation of a composite film, which transmitsvisible light energy and reflects infrared light energy on asubstrate:the improvement comprising respectively sputtering onto saidsubstrate a first transparent layer, a metallic layer, said metalliclayer substantially comprised of silver, and a second transparent layer,under sputtering conditions which produce discrete layers in thicknesseswhich provide cooperation between said layers to provide a compositefilm having significantly increased visible light energy transmissioncompared to said metallic layer alone and having high infrared lightenergy reflectivity.
 8. In the formation of a composite film, whichtransmits visible light energy and reflects infrared light energy, on asubstrate:the improvement comprising respectively sputtering onto saidsubstrate a first transparent layer, a metallic layer, said metalliclayer consisting essentially of silver, and a second transparent layer,under sputtering conditions which produce discrete layers in thicknesseswhich provide cooperation between said layers to provide a compositefilm having significantly increased visible light energy transmissioncompared to said metallic layer alone and having high infrared lightenergy reflectivity.
 9. In the formation of a composite film, whichtransmits visible light energy and reflects infrared light energy, on asubstrate:the improvement comprising respectively depositing onto saidsubstrate a first transparent layer, a metallic layer, said metalliclayer substantially comprised of silver, and a second transparent layer,under conditions which produce discrete layers in thicknesses whichprovide cooperation between said layers to provide a composite filmhaving significantly increased visible light energy transmissioncompared to said metallic layer alone and having high infrared lightenergy reflectivity.
 10. In the formation of a composite film, whichtransmits visible light energy and reflects infrared light energy, on asubstrate:the improvement comprising respectively depositing onto saidsubstrate a first transparent layer, a metallic layer, said metalliclayer consisting essentially of silver, and a second transparent layer,under conditions which produce discrete layers in thicknesses whichprovide cooperation between said layers to provide a composite filmhaving significantly increased visible light energy transmissioncompared to said metallic layer alone and having high infrared lightenergy reflectivity